Ligand engineering for active and durable, atomically-precise coinage-metal nanocluster catalysts
- 1Department of Chemistry, Graduate School of Science, The University of Tokyo, Tokyo 113-0033, Japan
Abstract
Metal nanoclusters (NCs) composed of fewer than 200 atoms have emerged as novel catalysts due to their specific physicochemical properties and structural fluxionalities, which differ significantly from those of the corresponding bulk or nanoparticles. Among the various types of NCs, those composed of coinage metals (Au, Ag, Cu) have garnered particular interest due to their relatively simple electronic structures and the discovery of size-specific catalysis by Haruta and Hutchings. Given the substantial alterations in the fundamental properties of coinage-metal NCs that result from the addition or removal of even a single atom, it is imperative to synthesize them with atomic precision to establish the structure-catalysis relationship and to maximize their potential in catalysis. The protection by organic ligands, such as thiolates, phosphines, alkynyls, and N-heterocyclic carbenes, plays a pivotal role in the precise control of NC size, the enhancement of NC stability against aggregation, and the determination of their geometric structures through single-crystal X-ray diffractometry. However, the ligand-protected metal NCs typically exhibit poor catalysis, primarily due to the absence of active sites for chemical transformation. A growing body of research has demonstrated that the employment of designed ligands facilitates the circumvention of the trade-off between activity and durability in the catalytic application of ligand-protected metal NCs. The application of ligand engineering facilitates the modulation of the geometry, density, and electronic structure of active sites. Furthermore, it enables the characterization of key intermediates through a range of spectroscopic methodologies. This review article provides a synopsis of recent examples of ligand engineering, with the objective of gaining deeper insight into catalytic mechanisms on coinage-metal NCs. This article also discusses prospects and challenges for the development of superior metal NC catalysts.
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BibTeX
@article{sakamoto2026ligand,
title = {{Ligand engineering for active and durable, atomically-precise coinage-metal nanocluster catalysts}},
author = {Kosuke Sakamoto and Shinya Masuda and Tatsuya Tsukuda},
journal = {Coordination Chemistry Reviews},
year = {2026},
month = jun,
doi = {10.1016/j.ccr.2026.218136},
url = {https://doi.org/10.1016/j.ccr.2026.218136},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Ligand engineering for active and durable, atomically-precise coinage-metal nanocluster catalysts
AU - Kosuke Sakamoto
AU - Shinya Masuda
AU - Tatsuya Tsukuda
PY - 2026
DA - 2026/06/05
JO - Coordination Chemistry Reviews
DO - 10.1016/j.ccr.2026.218136
UR - https://doi.org/10.1016/j.ccr.2026.218136
AB - Metal nanoclusters (NCs) composed of fewer than 200 atoms have emerged as novel catalysts due to their specific physicochemical properties and structural fluxionalities, which differ significantly from those of the corresponding bulk or nanoparticles. Among the various types of NCs, those composed of coinage metals (Au, Ag, Cu) have garnered particular interest due to their relatively simple electronic structures and the discovery of size-specific catalysis by Haruta and Hutchings. Given the substantial alterations in the fundamental properties of coinage-metal NCs that result from the addition or removal of even a single atom, it is imperative to synthesize them with atomic precision to establish the structure-catalysis relationship and to maximize their potential in catalysis. The protection by organic ligands, such as thiolates, phosphines, alkynyls, and N-heterocyclic carbenes, plays a pivotal role in the precise control of NC size, the enhancement of NC stability against aggregation, and the determination of their geometric structures through single-crystal X-ray diffractometry. However, the ligand-protected metal NCs typically exhibit poor catalysis, primarily due to the absence of active sites for chemical transformation. A growing body of research has demonstrated that the employment of designed ligands facilitates the circumvention of the trade-off between activity and durability in the catalytic application of ligand-protected metal NCs. The application of ligand engineering facilitates the modulation of the geometry, density, and electronic structure of active sites. Furthermore, it enables the characterization of key intermediates through a range of spectroscopic methodologies. This review article provides a synopsis of recent examples of ligand engineering, with the objective of gaining deeper insight into catalytic mechanisms on coinage-metal NCs. This article also discusses prospects and challenges for the development of superior metal NC catalysts.
SN - 0010-8545
SN - 1873-3840
ER -